Sensitized nitroparaffin



V 3,132,60 Patented May 5., 1964 3,132,060 SENSITHZED NITROZPARAFFIN Robert L. Beegle, In, Pasadena, Robert C. Brown, West Corina, and Claiborne M. James, San Dimas, Calii, assignors to Aerojet-Generai Corporation, Azusa, Califi, a corporation of Ohio No Drawing. 7 Filed May 16, 1961, fier. No. 110,332

-' 15 Claims. (Cl. 149-46) This invention relates to explosive compositions. In particular, this invention relates to explosive compositions containing nitroparatfins sensitized by organic amines.

7 The explosive compositions of this invention find particularly valuable application in quarrying where a powerful explosive having a high rate of detonation is required. The superior properties of our explosive compositions make them useful in mining, :for military purposes, in oil 'well production and in other applications where the use of explosives is necessary.

Explosives which can be handled in liquid form are known, however, they are subject to serious disadvantages only in this very sensitive state. plosives are dangerous to manufacture. Transportation of these sensitized explosives very difficult and requires extreme caution.

An object of this invention is to overcome the above" mentioned disadvantages of the prior Further ob I jeots and advantages become apparent hereinafter.

The .explosive compositions of this invention can be prepared by mixing, at'the site where the explosive is to be used, a sensitizer or mixture of sensitizers, such as 'lower alky-limine, arylalkyleneamine, monoethanolamine,

alkylphosphorousamide, aryldiamine, aminopyridine, N,

Ndiethyl-p-phenylenediamine, hydrazine, hydrazine compounds or alkylaryldiamine; and a nitroparafiin.

The followingexample is submitted to illustrate and not to limit the invention.

in that they are very sensitive to shock and are available Also, these known ex- EXAMPLE Qualitative Tests of Sefisitized Nitropamfiins The following tests were conducted using sensitized 5 nitromethane. The leach tests were carried out by treq'uently shaking mixtures containing about equal volumes of solutions of sensitizer. in nitromethane and water or aqueous sodium chloride solution, the aqueous sodium chloride solutions were prepared to simulate sea water. After frequent shaking for the time noted in the table, the aqueous and nitrometh-ane mixtures were -=a1lowed to stand In the detonation procedure No. l, samples of sensitized nitrornethane solution were placed in x 150 mm. Pyrex glass test tubes. The test tubes were placed behind a safety shield and detonated with a No. 6 or 8 hlasting cap or a Chestnut Booster (hereafter designated, C. B.). A Chestnut Booster is an electrical blasting cap which has two pieces of detonating fuse two or three inches long, such as Primacond, manufactured -by Ensign- Brickford, taped to its sides. The ends of the detonating 'fuse which project over the end of the blasting cap are cut at about a angle .to the longitudinal axis of the fuse. The cut faces are then taped together. When detohated, the point of juncture between the two fuses produces a very sharp shock. The use of this type of booster is sometimes necessary where the charge of sensitized nitroparaflin is not tightly restricted.

In detonation procedure No. 2, '15 cc. samples of sensitized nitromethane solution were placed in 10 x mm. fPyrex glass test tubes. The test tubes were placed in a piece of steel tubing having an inside diameter just large enough to receive the test'tuhes. The composite containers holding sensitized 'nitromethane were placed behind a safety shield and fired withblasting caps or a CB. The results of the qualitative tests are set forth in the table TA BL E .-TEST RESULTS Sensitizer Detona- Number tion pro- Detonator Number of deto- Leach solution Leach ceigure of tests nations time Propylene diamitne Ethylene diamine..- Hydra-zine N,N-dimethyl hyd Ethylene diamine Propylene diamine a-n- Hucommons-moo 0000mm:- more oooooocaoonawn rewrote-Microfilm Dist. water 4 Aqueous sodium 4 chloride. 4

'Aqueous sodium 4 chloride. None Dist. water 4 Aqueous sodium 4 chloride 4 4 chloride.

TABLE.TEST RESULTS-Continued Oonccu- Detona- Number Sensrtrzer tration, tion pro- Detonator Number of deto- Leach solution Leach Weight ccdure of tests nations time percent N 0. (1111s,)

Benzylamm9-- 6 1 8 7 Aqueous sodium 24 chlor' c. 8 1 8 7 (1o 24 6 1 8 6 Dist. wat'cr 72 8 1 8 6 Aqueous sodium 72 chloride. 6 2 8 8 None 6 2 6 Dist. water 4 6 2 5 5 Aqueous sodium 24 chloride. 6 2 5 5 d 8 2 5 5 Dist. Water. 4 1 12 8 None 6 1 12 d 6 1 6 3 Dist. water 6 1 8 5 Aqueous sodium 24 chloride. 6 1 7 5 Dist. water 24 6 1 10 9 do 72 6 1 10 8 Aqueous sodium 72 chloride. 6 1 9 5 Dist. Water 4 6 l 6 1 Aqueous sodium 4 chloride. 6 2 8 8 None 6 2 5 5 Aqueous sodium 24 chloride. (3 2 5 5 Dist. Water 24 6 2 5 4 Aqueous sodium 72 chloride. 6 2 5 5 Dist. water 4 1 18 12 None 6 1 8 7 do 6 1 8 4 Dist. water 4 6 1 9 9 Aqueous sodium 4 chloride. 6 2 8 8 None 6 2 5 5 Dist. water v 4 6 V 2 5 5 Aqueous sodium 4 chloride. 6 2 5 5 Dist. water- 24 6 2 5 4 Aqueous sodium 24 chloride. 6 2 3 3 Dist. water. 72 6 2 3 3 A ueous sodium 72 1 5 0 2 5 0 2 5 0 2 l 3 0 2 1 3 0 4 1 3 0 2 1 3 0 4 1 3 0 4 1 3 0 4 1 3 0 Benzydine 4 1 3 0 In addition to those compounds set forth in the specific examples, the following compounds are sensitizers, when used alone or in a mixture with one another, within the scope of our invention:

N,N,N'-triethyl hydrazine N,N'-diphenyl hydrazine N-phenyl-N-methyl hydrazine Benzyl hydrazine Nitroparaifins which find valuable application, when used alone or in mixtures with one another, within the scope of this invention, include the following:

Mononitromethane 1- or 2-nitropropane Symmetrical dinitroethane 1,3-dinitropropane 1,1,3 -trinitrobutane Nitroethane 1,1,2-trinitroethane The nitroparafiins used in this invention will preferably have a slight negative oxygen balance. For this reason when mixtures of nitroparaifins are used it is necessary to select and proportion the nitroparaffins which make up the mixture so that the mixture will have a slightly negative oxygen balance.

Our preferred nitroparaffin is mononitromethane because it has an oxygen balance which renders it relatively safe to handle when unsensitized, it has a low freezing point, it can be stored safely and when sensitized can be detonated with a standard blasting cap.

The sensitizers of this invention can be employed in concentrations from about 0.5% to about 20% by weight plosion.

of the solution of sensitizer and nitroparaffin. Preferably,the.sensitizer is present in the amount of about 2% to about by weight of the solution of sensitizer and nitroparaiiin, since large amounts tend to dilute and reduce the explosive power of the nitroparafiin.

Preferably the sensitizer andnitroparafiin are stored,

handled and transported in separate containers, being mixed together only at the time and place where they are to be used. This procedure provides a very safe method for working with a very powerful explosive, since unsensitized nitroparaflins can be handled safely with only the precautions normally used in handling parafiins are very stable to shock, being almost impossible to detonate without the use of a booster, such as an "electric blasting cap, they can be handled and stored with safety if the standards of safety normally employed with explosives are observed.

The sensitizer and nitroparaffin'can be mixed in any manner and vessel desired. As will be understood in the art, the 'use of equipment which is likely to give 01? Various fillers can be included in the sensitized nitroparaflin before or after it is sensitized. Such fillers include sawdust, powdered coal or carbon, starch, etc. Fillers are well-known in the art.

Since the nitroparaffins and sensitizers alone or in ad-' mixture with one another have very low freezing points .-the sensitized nitroparaflin explosives are particularly well suited for use in cold weather operations and where thematerials must be stored in unheated areas. If accidentally frozen, the sensitized nitroparaffins can be thawed out with very little danger of an untimely ex- While' it is preferable not to overheat either the sensitized nitroparafiins or the separate sensitizer and nitroparafiins, it is possible to store either sensitized 'or unsensitized materials at temperatures up to about 120 F. for an indefinite period of time without detrimental effect. II Detonation of sensitized nitroparaflins can be accom- V plished by any booster means, such as electric blasting caps or 'a Chestnut Booster.

Booster means are well known in the art. Multiple boosters can be used, if

. desired. .For' large charges a small charge of some other explosive, such as dynamite, can be used as a booster.

I Sensitized nitroparafiins can be contained in place at the site of use by conventional metal, plastic, wood, pa-

per, etc., containers. If the charge is to be placed in a hole bored in a solid rock formation, such as granite,

then the liquid sensitized nitroparafiin can be poured directly, into the hole without the use of any other container. The sensitized nitroparaflins can be packaged in receptacles which serve as storagecontainers and also serve to contain the charge in place at the site of use.

When the sensitized nitroparaflins of this invention are usedin oil wells to fracture oil bearing formations,

iit is'necessary to use a sensitizer which will not be leached out or in some manner inactivated by the aqueous conditions sometimes present in oil wells.

I Water or dampness often come in contact with explosives during storage or just prior to use in many applications, so it is desirable that sensitizers be available which are not inactivated by water. Even though they by water.

' sensitizer is present in an amount from about 2% to ,are to some extent water soluble, benzylamine, 2,4-

toluenediamine and 2,6-diaminopyridine sensitizers are not leached out of sensitized nitroparaffins or inactivated Nitroparaffins sensitized with these sensitizers can be poured through water and still be detonated.

These sensitizers are preferred where the charge is to be exposed to water. I I

It will be understood thatvarious modifications can be made in this invention without departing from the spirit thereof or the scope of the claims.

.We claim: I

1. An explosive composition comprising sensitizer in an amount from about 0.5 to about 20% by weight, saidsensitizer being selected from the group consisting of lower alkyleneimine, arylalkyleneamine, monoethanolamine, alkylphospho'rousamide, aryldiamine, aminopyrisensitizer is a mixture of compounds selected from said group.

3. The explosive composition of claim 1, wherein said about 10% by weight.

,4. The explosive composition of claim 1, wherein said nitroparafiin is nitromethane. I

5. An explosive composition comprising ethylene imine in an amount from about 0.5% to about 20% by weight and nitroparafiin. I

6. An explosive composition comprising hydrazine in an amount from about 0.5% to about 20% by weight and nitroparaffin.

7. An explosive composition comprising monoethanolamine in an amount from about 0.5 to about 20% by weight and nitroparafiin.

8. An explosive composition comprising hexamethyl phosphorous triamine in an amount from about 0.5% to about 20% by weight and nitroparaflin.

9. An explosive composition comprising N,N-dimethyl hydrazine in an amount from about 0.5 to about 20% by weight and nitroparaflin.

I 10. An explosive composition comprising sensitizer in an amount from about 0.5% to about 20% by weight,

said sensitizer being selected from the group consisting of lower alkyleneimine, arylalkyleneamine, monoethanolamine, alkylphosphorousamide, aryldiamine, aminopyridine, hydrazine, lower alkyl hydrazine and alkyldiamino benzene; nitroparafiin and inert filler.

11. An explosive composition comprising, by weight, 20% to 0.5% of benzylamine, and to 99.5% nitromethane.

12. An explosive composition comprising, by weight, 20% to 0.5% 2,4-'toluene diamine, and 80% to 99.5% nitromethane.

13. An explosive composition comprising, by weight, 20% to 0.5 2,6-diami'no pyridine, and 80% to 99.5 nitromethane.

14. An explosive composition comprising nitromethane and a monoarylalkyleneamine sensitizer in anamount from about 0.5% to about 20% by weight.

15. The explosive composition of claim 14 wherein said monoarylalkyleneamine is present in an amount from about 2% to about 10% by weight.

References Cited in the file of this patent UNITED STATES PATENTS Canada June 3, 1958 

1. AN EXPLOSIVE COMPOSITION COMPRISING SENSITIZER IN AN AMOUNT FROM ABOUT 0.5% TO ABOUT 20% BY WEIGHT SAID SENSITIZER BEING SELECTED FROM THE GROUP CONSISTING OF LOWER ALKYLENEIMINE, ARYLALKYLENEAMINE, MONOETHANOLAMINE, ALKYLPHOSPHOROUSAMIDE, ARYLDIAMINE, AMINOPYRIDINE, HYDRAZINE, LOWER ALKYL HYDRAZINE AND ALKYLDIAMINO BENZENE;; AND NITROPARAFFIN. 